In this paper, microlens array (MLA) templates with high filling factors were prepared by combining a thermal reflow method and parylene chemical vapor deposition (CVD). Then photoresist MLAs were replicated from the MLA templates by using ultraviolet nanoimprint technology. The surface morphology of the replicated photoresist MLAs was characterized by scanning an electron microscope and optical microscope. Results show that the photoresist MLAs have a relatively smooth surface, and the filling factor has been improved obviously. Also, the surface profiles of the MLAs were measured. The optical imaging properties of the MLAs were also characterized, and they had a relatively good imaging performance. Finally, the photoresist MLAs were applied on organic LEDs (OLEDs), and their luminance and current efficiencies were measured. Results show that the current efficiency of the OLEDs increased by about 42.41%, 29.01%, and 35.51%, respectively, for OLEDs with circular, hexagonal, and square MLAs. All the results above indicate that it is a simple and effective process to prepare MLA templates with high filling factors by combining thermal reflow and CVD techniques, and the prepared photoresist MLAs have great application potential in OLED areas.